Polyamide, polyimide, and polyamide-imide polymers of diamino-t-butylbenzene

ABSTRACT

Resinous condensation polymers of polycarboxylic acid compounds and aromatic diprimary amines comprising diamino-t-butylbenzenes are described. In particular, film-forming polyamides, polyimides and polyamide-imides and their copolymers made using diamino-t-butylbenzenes which have amino groups meta or para to each other on a benzene ring are described. These polymers have some solubility in organic solvents such as N-methylpyrrolidone, a high glass transition temperature, excellent thermal stability, and are useful in films, fibers and composites, and in the electronics industry as electrical component substrates, protective coatings, interlevel dielectrics and the like.

REFERENCE TO RELATED APPLICATION

This is a division of application Ser. No. 277,756, filed Nov. 30, 1988,now abandoned, which is a CIP of 212,510, filed June 28, 1988, now U.S.Pat. No. 4,946,934.

BACKGROUND OF THE INVENTION

This invention relates to resinous condensation polymers ofpolycarboxylic acid compounds and aromatic diprimary amines comprisingdiamino-t-butylbenzenes. More particularly, this invention relates tosoluble, film-forming polyamides, polyimides and polyamide-imides madeusing diamino-t-butylbenzenes which have amino groups meta or para toeach other on a benzene ring.

Aromatic polyamides, polyimides and polyamide-imides have foundextensive use in industry as fibers, composites, molded parts anddielectrics due to their toughness, flexibility, mechanical strength andhigh thermal stability, and, in the case of polyimides, their lowerdielectric constant and high electrical resistivity. Such polymers havebeen used in both film and coating form as advanced materials for suchuses as passivation and insulating coatings, interlevel dielectrics, dieattach adhesives, flexible circuit substrates, and the like.

Although current polyamides, polyimides, and polyamide-imides made from,for instance, metaphenylenediamine have the toughness, flexibility andthermal stability necessary to meet the rigorous processing andoperating conditions required for certain uses, they do not exhibit thelow dielectric constant and reduced moisture uptake shown by lowerthermal stability polymers such as polyethylene andpolytetrafluoroethylene. The latter polymers, however, are not usefuldespite their excellent dielectric and moisture uptake properties ifthermal stability requirements are demanding. A further difficultylimiting the usefulness of polyethylene and polytetrafluoroethylene isdue to to their insolubitity in commercial organic solvents.

In addition, many of these applications require deposition of polymerfrom a solvent in order to form a thin film having the desiredproperties. Unfortunately, many polyamides, polyamide-imides andparticularly polyimides are generally insoluble even in solvents likeN-methyl pyrrolidone or N,N-dimethylacetamide which inhibits theirusefulness in important areas.

OBJECTS OF THE INVENTION

A general object of this invention is to produce a new resinouscondensation polymer of a polycarboxylic acid compound and an aromaticdiprimary amine comprising a diamino-t-butylbenzene useful as afilm-forming polymer.

Another general object of this invention is to produce a new resinouscondensation polymer composition exhibiting a combination of lowdielectric constant, low moisture uptake, partial solubility in highlypolar organic solvents, and thermal stability.

A more specific object of this invention is to provide improvedpolyamides, polyimides, and polyamide-imides made usingdiamino-t-butylbenzenes which have amino groups meta or para to eachother on the benzene ring.

Other objects and advantages of the invention will become apparent uponreading the following detailed description and appended claims.

SUMMARY OF THE INVENTION

The general objects of this invention can be attained with a resinouscondensation polymer of a polycarboxylic acid compound and an aromaticdiprimary amine comprising a diamino-t-butylbenzene. In preferredpolymers of this invention the diprimary amine is at least onediamino-t-butylbenzene having amino groups meta or para to each other onthe benzene ring.

In another aspect, the invention is an at least partially soluble,film-forming polyamide, polyimide, and polyamide-imide of anappropriately selected polycarboxylic acid compound and at least onediamino-t-butylbenzene selected from the group consisting of2,4-diamino-t-butylbenzene, 2,5-diamino-t-butylbenzene,2,6-diamino-t-butylbenzene, and 3,5-diamino-t-butylbenzene.

DETAILED DESCRIPTION OF THE INVENTION

The condensation polymers of the present invention can be prepared froman appropriately selected polycarboxylic acid compound and an aromaticdiprimary amine comprising a diamino-t-butylbenzene.

The polymers of this invention are polyamides when they are formed byreaction of the diamino-t-butylbenzene with carboxylic diacids,diesters, and diacyl chlorides. Suitable carboxylic acid compoundsinclude terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylicacid, 5-t-butylisophthalic acid, the dimethyl ester of2,6-naphthalenedicarboxylic acid, etc., the diacyl chlorides of benzene,t-butylbenzene, biphenyl, diphenylether, and naphthalene. Preferably,the polyamide is made from the diacyl chloride of biphenyl,t-butylbenzene, diphenylether, or naphthalene. More preferably, thepolyamide is made from 5-t-butylisophthaloyl dichloride or 2,6-naphthoyldichloride.

The polymers of this invention are polyimides when they are formed byreaction of the diamino-t-butylbenzene with aromatic dianhydrides ortheir corresponding carboxylic acids or esters. The aromaticdianhydrides useful in this invention include the symmetricaldianhydrides of benzene (PMDA), naphthalene, biphenyl (BPDA),diphenylether (OPAN), benzophenone (BTDA),bis(3,4-dicarboxyphenyl)sulfone dianhydride (SPAN),2,2-bis(3,4-dicarboxyphenyl)propane dianhydride (IPAN), or2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA).Preferred polyimides of this invention are made from the symmetricaldianhydride of biphenyl tetracarboxylic acid or diphenylethertetracarboxylic acid, 2,2-bis(3,4-carboxyphenyl)propane dianhydride, or2,2-bis(3,4-carboxyphenyl)hexafluoropropane dianhydride. Morepreferably, the polyimide is made from2,2-bis(3,4-carboxyphenyl)hexafluoropropane dianhydride.

The polymers of this invention are polyamide-imides when they are formedby reaction of the diamino-t-butylbenzene with the acyl chloride oftrimellitic acid anhydride (TMAC), or mixtures of di and tetrafunctional polycarboxylic acid compounds.

All of these resinous condensation polymers are at least partiallysoluble in highly polar organic solvents such as N-methylpyrrolidone(NMP), gamma-butyrolactone (GBL), and N,N-dimethylacetamide (DMAC). Thesolubility of these polymers provides processability, for example, infilm-forming. Typically, polymer concentrations upward from about 1weight percent are useful in film-forming using highly polar solvents.Any particulates or insolubles in the polymer due to formation of a gelor cross-linking can be partitioned out, for example, by filtration,before casting.

Briefly, the resinous condensation polymers of this invention can bemade by any technique used in the prior art to form polyamide,polyimide, and polyamide-imide polymers provided the aromatic diprimaryamines employed comprise at least one diamino-t-butylbenzene.

Diprimary amines useful in this invention includediamino-t-butylbenzenes which have amino groups meta or para to eachother on a benzene ring, i.e., 2,4-diamino-t-butylbenzene (2,4-DATB),2,5-diamino-t-butylbenzene (2,5-DATB), 2,6-diamino-t-butylbenzene(2,6-DATB), and 3,5-dimaino-t-butylbenzene (3,5-DATB).

Polyamide, polyimide and polyamide-imide polymers made from3,5-diamino-t-butylbenzene are described and claimed in applicationSerial No. 212,510, filed on June 28, 1988, in the names of David J.Fenoglio, Douglas E. Fjare, Edwin F. Morello and Neal R. Nowicki, whichis hereby incorporated by reference.

In the formation of resinous condensation polymers of this invention, adiamino-t-butylbenzene may be used alone or in conjunction withaliphatic diamines or other aromatic diamines. Suitable aliphatic aminescontain 2 to about 12 carbon atoms, e.g., ethylenediamine,trimethylenediamine, hexamethylenediamine, dodecamethylenediamine, etc.In those cases where an aliphatic diamine containing 3 to 12 carbonatoms comprises more than 10 to 20 weight percent of the diprimaryamine, the reaction product has a lower melting point and/or highersolubility than product produced from all aromatic amines.

Suitable aromatic diamines include metaphenylenediamine, oxybisaniline,methylenebisaniline, 4,4'-diaminodiphenyl propane,diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone,3,4'-diaminodiphenylsulfone, 4,4'-diaminobenzopheneone, toluenediamine,metaxylene diamine, etc. Generally, the diamino-t-butylbenzene can rangefrom about 5 mol % to 100 mol %, preferably at least 20 mol %, of thetotal diamines. Typically, for best results it is preferable to use onlyaromatic diamines since the thermal properties of the polymers decreasewhen aliphatic diamines are employed.

The diamino-t-butylbenzene can be any reasonably pure source ofdiamino-t-butylbenzene, preferably polymer grade having a purity of 98%or higher. For example, a suitable 2,4-diamino-t-butylbenzene isprepared by a process comprising nitration of t-butylbenzene, recoveryand purification of 2,4-dinitro-t-butylbenzene, as, for example, bywashing, extraction and/or crystallization using water and/or organiccompounds such as alkanes or alcohols, hydrogenation of purified2,4-dinitro-t-butylbenzene, recovery and purification of4-(t-butyl)-1,3-phenylenediamine, and recovery and, if desired,purification of 2,4-diamino-t-butylbenzene. Hexane and ethanol arepreferred organic compounds used in purifications by washing, extractionand/or crystallization. Typically, best results are obtained when thesource of 2,4-diamino-t-butylbenzene used is chosen to reduce thecontent of foreign aromatic compounds in the reaction mix.

In somewhat greater detail, polymers of this invention are preferablymade by dissolving aromatic diamine, preferably polymer grade diamine,in a solvent such as N-methylpyrrolidone or N,N-dimethylacetamide andadding carboxylic acid compound at a temperature between about 0° C. and100° C., preferably in a range from about 10° to about 40° C., to make asolution of the polyamic acid polymer. When polyimide or polyamide-imidepolymers are made, a second stage of reaction is required to imidize theamic acid groups. Imidization can be accomplished either thermally,preferably at a temperature in a range from about 200° to about 400° C.,or chemically, preferably using pyridine and acetic anhydride.Typically, solutions of the polyamic acid polymer from about 5 to about50 weight percent, preferably, about 10 to about 40 weight percent, areemployed.

In general, the molar ratio of diamine to polycarboxylic acid compoundcan range from about 1.2:1 to about 1:1.2. However, best results areattained using substantially equal molar portions of the diamine and thecarboxylic acid compound in making the polymer, although a small excessof one or the other component, or even a monofunctional compound, can beused in order to terminate the polymer with either carboxylic acid oramine groups to control molecular weight.

The resulting solution of polymer can be spread on a substrate, and thesolvent evaporated leaving the polymer in the form of a layer orcoating. Any particulates or insolubles in the polymer due to formationof a gel or crosslinking can be partitioned out, for example, byfiltration, before coating. The coating or film in the case of apolyimide is then heated, preferably in an inert gas such as nitrogen,to complete the imidization process. Films and coatings of the polymersare desirably thin, preferably between about one and about twentymicrons in thickness, more preferably between about one and about tenmicrons.

The polymers of this invention are useful as fibers, composites and thelike, and both free-standing films and coatings can be made in the formof flexible substrates for electrical components, interleveldielectrics, passivation, etc.

The polyamides, polyimides, and polyamide-imides of this invention havehigh glass transition temperature, preferably above about 300° C., hightemperature of onset of degradation in nitrogen, preferably above about450° C., at least partial solubility in organic solvents, preferably atleast about fifteen weight percent in N-methylpyrrolidone for thepolyamides, preferably at least about ten weight percent inN-methylpyrrolidone for the polyamideimides, and preferably at leastabout one weight percent in N-methylpyrrolidone for the polyimides. Theyalso have lower density, preferably at least less than 1.3 g/cc, andlower uptake of moisture at 100% relative humidity (R.H.), preferablyless than about two weight percent for the polyimides, preferably lessthan about five weight percent for the polyamide-imides, and preferablyless than about eight weight percent for the polyamides.

The following Examples will serve to illustrate certain embodiments ofthe herein disclosed invention. These Examples should not, however, beconstrued as limiting the scope of the novel invention as there are manyvariations which may be made thereon without departing from the spiritof the disclosed invention, as those of skill in the art will recognize.

EXAMPLES General

All percents used are weight percents. Test procedures used tocharacterize the polymers of this invention are are follows:

Dielectric Constant

Measurements of dielectric constant were made on thin films (0.7 to 2mils thick) cast from polyamic acid solutions onto glass plates andthermally cured. The measurements were made using a two-fluid celltechnique as described in ASTM D150. The reproducibility of thedielectric constant measurement using this technique is about ±2%.

Moisture Absorption and Change in Dielectric Constant

Moisture absorption measurements were made on wafer-level capacitorstructures. Three-layer structures of aluminum/polymer/aluminum werefabricated on silicon wafers as set forth in U.S.S.N. 212,511, filed onJune 28, 1988. Aluminum thickness was 0.6 microns, polymer thickness was1 to 2 microns, and capacitor size was 0.01 square centimeters.Capacitance of the structures was measured between 50° C. and 300° C.over a range of frequencies. The capacitors were tested to 300° C.,allowed to cool, and immediately reheated to 300° C. The moistureabsorption values were calculated based on the difference between themeasured 1 MHz dielectric constants at 50° C. for the first and secondheats of the test according to the formula:

    Equilibrium Moisture (100% R.H.)≅2Δε/0.4

which formula is based upon 2 percent equilibrium moisture per unitchange in epsilon, and where Δε is the change in dielectric constantbetween first and second heat. The start of the first heat is assumed tobe at 40% R.H. as the wafers were allowed to equilibrate for two days at40% R.H. prior to testing. The start of the second heat is assumed to beapproximately 0% R.H. as the wafers were reheated immediately after thewater was driven off during the first heat. The change in dielectricconstant at 40% R.H. is the percent difference between the measured 1MHz dielectric constants at 50° C. for the first and second heats of thetest.

Glass Transition Temperature

The glass transition temperature (T_(g)) of the polymers was measured bydifferential scanning calorimetry. A temperature ramp rate of 20° C./minwas used for all determinations.

Temperature of Onset of Degradation

The temperature of onset of degradation (TGA) of the polymers wasmeasured by thermogravimetric analysis in air and nitrogen. The onsettemperature is the temperature at which 1 weight percent weight loss isfound at a heating rate of 10° C./min. Measurements were made on thinfilms cast from polymer solutions onto glass plates and thermally cured.

EXAMPLE 1

In this and following examples the 3,5-diamino-t-butylbenzene used wasprepared form 5-t-butylisophthalic acid by the improved processdescribed and claimed in application Ser. No. 249,656, filed on Sept.27, 1988, in the name of Douglas E. Fjare, which is hereby incorporatedby reference.

In a flame dried two liter 3-necked round bottomed flask equipped with athermometer-nitrogen inlet tube and stirred was placed 19.68 g (0.12mol) of 3,5-diamino-t-butylbenzene and 275 g of dimethylacetamide. Thiswas mixed and cooled under nitrogen to 10° C. Solid5-t-butylisophthaloyl chloride, 31.08 g (0.12 mol) was added with mixingover 30 min while a temperature of no greater than 10° C. wasmaintained. The mixture was allowed to come to room temperature withmixing and heated to 30°-35° C. for 3 hr. The resulting polymer wasprecipitated and washed in water. After drying, 41 g (97.6% yield) of awhite, powdery solid was obtained. This material has an inherentviscosity of 0.70 in dimethylacetamide (0.4 wt.%) at 30° C. The glasstransition temperature was found to be 322° C. as measured by DSC.Thermal gravimetric analysis in nitrogen shows decomposition at 431° C.The density of this polyamide was determined to be 1.078 using densitygradient columns.

EXAMPLE 2

In a manner similar to Example 1 above, 16.43 g of3,5-diamino-t-butylbenzene was reacted with 20.3 g of terephthaloyldichloride in 93.7 g of dimethylacetamide. The resulting polyamide hasan inherent viscosity of 1.63. The glass transition temperature of thepolymer is 337° C.

EXAMPLE 3

In a manner similar to Example 1, 19.68 grams of3,5-diamino-t-butylbenzene was reacted with 24.36 grams of isophthaloyldichloride in 250 g of dimethylacetamide. The resulting polyamide has aninherent viscosity of 0.55. The glass transition temperature of thepolyamide is 300° C.

EXAMPLE 4

To a clean and dry 100 mL reaction kettle were added 5.402 grams of3,5-diamino-t-butylbenzene and 14.611 grams of2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydried; alloperations were performed under a nitrogen atmosphere. To the monomerswere added 59.99 grams of N-methylpyrrolidone and the resulting mixtureswas stirred for 17 hours. The resulting polyamic acid solution contained25% by weight solids and has an inherent viscosity of 1.06 dL/q at 25°C. The solution was refrigerated until needed.

A film of the 6FDA/3,5-DATB polyamic acid was prepared by casting theresin onto a soda-lime glass in a dust-free environment. The polyamicacid film was thermally imidized to the corresponding polyimide film byheating in a forced-air oven for one hour at 80° C., then 200° C., andfinally 300° C. The resulting film was removed from the glass plateafter cooling to room temperature by soaking in water. The dielectricconstant of the dried polyimide film is 2.77 (0% R.H.) at 1 MHz.

EXAMPLE 5

A copolyimide having the composition 1 6FDA: 0.8 3,5-DATB : 0.2 APBP wasprepared in the following manner. A mixture of 2.028 grams of 3,5-DATBand 1.135 grams of 4,4'-bis(p-aminophenoxy)biphenyl (APBP) was dissolvedin 15.057 grams of N-methylpyrrolidone and reserved. In a separatekettle, 6.842 grams of 6FDA was dissolved in 34.869 grams ofN-methylpyrrolidone. The mixed diamines solution was added over a periodof 30 minutes to the 6FDA solution with stirring. An additional 6.748grams of N-methylpyrrolidone were added to the solution. Allmanipulations were performed under a nitrogen atmosphere. The resultingcopolyimide solution was 15.0% solids and showed an inherent viscosityof 0.92 dL/g at 25° C.

EXAMPLE 6

Into a dry flask containing a nitrogen atmosphere were added 28.21 g ofdimethylacetamide and 4.14 g of 3,5-diamino-t-butylbenzene. To thisstirred solution was added 5.264 g trimellitic anhydride acid chloridewhile maintaining the temperature between 20° and 30° C. After additionwas complete, the solution temperature was maintained at 30° C. for anadditional 5 hours. The resulting polymer was precipitated in a highspeed blender and washed in distilled water to a pH of 4.5. After airdrying, the polymer was vacuum dried at 60° C. to give 8.1 g of apowdery solid in 96% yield. The initial inherent viscosity was 0.167;after curing 30 minutes at 260° C., the inherent viscosity was 0.278 asmeasured at 25° C. in dry N-methylpyrrolidone with a Cannon-Fenskeviscometer at a 0.5 g/100 mL concentration. Tg of the polymer is 331° C.and temperature of onset of degradation under nitrogen is 446° C.Polymer density is 1.33 g/mL.

EXAMPLE 7

In a manner similar to Example 6, a TMA end-capped polymer was preparedfrom 7.09 g of oxybisaniline, 2.46 g of 3,5-diamino-t-butylbenzene, 10 gof trimellitic anhydride acid chloride, and 0.48 g of trimelliticanhydride in 50 mL of dimethylacetamide. The initial inherent viscosityof the polymer was 0.294; after curing 30 minutes at 260° C., theinherent viscosity was 0.538.

EXAMPLE 8

Some physical properties of the polyimides of this invention are givenin Table I below.

                  TABLE I                                                         ______________________________________                                        Physical Properties of Films and Wafer Level                                  Coatings of Some 3,5-DATB Polyimides and Copolyimides                                                            Temper-                                           Dielectric Moisture         ature of                                          Constant   Absorption       Onset of                                   Dian-  at 0% R.H. (Wafer     T.sub.g                                                                             Degradation                                hydride                                                                              and 1MHz   Level) (%) (°C.)                                                                        in N.sub.2 (°C.)                    ______________________________________                                        OPAN   3.18       1.2        291   510                                        IPAN   2.99       1.9        309   473                                        6FDA   2.77       0.7        310   486                                        6FDA.sup.1                                                                           2.97       0.8        349   458                                        6FDA.sup.2                                                                           3.07       --         296   467                                        ______________________________________                                         .sup.1 Copolymer of 3,5DATB and 4,4'-bis(paminophenoxy)biphenyl               .sup.2 Copolymer of 3,5DATB and 4,4'-diaminodiphenylether                

EXAMPLE 9

In this example 2,4-diamino-t-butylbenzene was prepared fromt-butylbenzene by a process comprising nitration and hydrogenation.

A mixed acid nitrating medium was prepared containing nitric acid (196.1g of 70% HNO₃) and sulfuric acid (437.2 g of conc. H₂ SO₄). Thent-butylbenzene (268 g, 2.0 moles) was placed into a flask and cooled toa temperature below 5° C. and vigorously stirred while the nitratingmedium was added to the flask over a 20 min period. After an additional30 min period of mixing at a temperature below 5° C., mixture wasallowed to separate and the aqueous (bottom) layer was drawn off anddiscarded. This nitration process was repeated at a temperature below45° C. using a mixed acid nitrating medium containing nitric acid (392.2g of 70% HNO₃) and sulfuric acid (874 g of conc. H₂ SO₄).

The organic product was washed with water, then slurried with 500 mL ofhexane at a temperature of 60° C. and filtered. The product wascrystallized from ethanol. After drying, 359 g of2,4-dinitro-t-butylbenzene was recovered, 80% of theoretical for thenitration step.

A portion of this 2,4-dinitro-t-butylbenzene (100 g), ethanol (500 mL)and a hydrogenation catalyst (1.25 g of 10% Pd/C) were placed in aone-liter autoclave which was purged with nitrogen and pressurized to600 psig with hydrogen. The temperature of the autoclave containing thereaction slurry was raised to 100° C. and held at 100° C. for 45 min tocomplete the reduction reaction.

After the autoclave cooled to room temperature and the pressurereleased, the solution was filtered to remove the solid catalyst and acrude product was recovered from the solvent by stripping under vacuum.

This crude product was slurried with hot hexane, then cooled andscratched to initiate crystallization. The crystals were filtered torecover 59.37 g (81% yield) of purified4-(t-butyl)-1,3-phenylenediamine. The melting range of this productmeasured 62°-65° C. Product prepared as in this example was used as thesource of 2,4-diamino-t-butylbenzene in the following examples.

EXAMPLE 10

Into a flame dried 300 mL 3-necked round bottomed flask equipped with athermometer, nitrogen inlet tube and stirrer were placed 9.84 g (0.06mole) of 2,4-diamino-t-butylbenzene and 147 g of N,N'-dimethylacetamide.The contents of the flask were mixed and cooled to 10° C. undernitrogen. Solid terephthaloyl chloride, 12.18 g (0.06 mole), was addedwith mixing over 20 minutes while a temperature below 10° C. wasmaintained. The contents of the flask were allowed to come to roomtemperature with mixing and then heated to a temperature in the range of30°-35° C. for three hours. The resulting polymer was precipitated andwashed in water. After drying, 16.6 g (94% yield) of a white powderysolid was obtained. This material had an inherent viscosity of 0.41 inN,N'-dimethylacetamide (0.4 wt. %) at 30° C. The glass transitiontemperature was 331° C. as measured by DSC. Thermal gravimetric analysisin nitrogen shows 1% decomposition at 373° C. To increase the inherentviscosity, the powdered polymer was heated at 325° C. under vacuum (0.1mm) for 24 hours. The resulting polyaramide had an inherent viscosity of0.86 and a glass transition temperature of 334° C.

EXAMPLE 11

In a manner similar to Example 10 above, 9.84 g of2,4-diamino-t-butylbenzene was reacted with 12.18 g of isophthaloyldichloride in 147 g of dimethylacetamide. The resulting polyamide had aninherent viscosity of 0.24 and a glass transition temperature of 283° C.After thermal treatment the polyamide had an inherent viscosity of 0.51and a glass transition temperature of 292° C.

EXAMPLE 12

In a manner similar to Example 10, 9.84 g of 2,4-diamino-t-butylbenzenewas reacted with 15.54 g of 5-t-butyl isophthaloyl dichloride in 137.5 gof dimethylacetamide. The resulting polyamide had an inherent viscosityof 0.33 and a glass transition temperature of 292° C. After thermaltreatment the polyamide had an inherent viscosity of 0.82 and a glasstransition temperature of 298° C.

EXAMPLE 13

Into a flame dried 300 mL 3-necked round bottomed flask equipped with athermometer, nitrogen inlet tube, stirrer and pressure equalizingdropping funnel (with drying tube) were placed 9.84 g (0.06 mole) of2,4-diamino-t-butylbenzene and 117 g of N,N'-dimethylacetamide. Thecontents of the flask were mixed and cooled to 10° C. under nitrogen.Then 10.98 g (0.06 mole) of adipoyl chloride were slowly added to themixture over a 15 min period during which the flask was maintained attemperature below 10° C. The contents of the flask were allowed to cometo room temperature with mixing and then heated to a temperature of 40°C. and held at 40° C. for 3 hrs. The resulting polymer was thenprecipitated and washed in water. After drying, 14.25 g (87% yield) of awhite powdery solid was obtained. The material had an inherent viscosityof 0.27 in N,N'-dimethylacetamide (0.4 wt. %) at 30° C. The glasstransition temperature was found to be 182° C. as measured by DSC.Thermal gravimetric analysis in nitrogen shows 1% decomposition at 347°C. Heat treatment of this powdered polymer produced an increase ininherent viscosity. The best result was to heat the polymer at 200° C.under vacuum (0.1 mm) for 24 hrs. This gave an inherent viscosity of0.34. The resulting glass transition temperature was 183° C.

EXAMPLE 14

In this example a polyimide polymer was made by reacting2,4-diamino-t-butylbenzene with 3,3',4,4'-tetracarboxybiphenyldianhydride. The property enhancements observed for this polymer arealso obtained in polymers made with other aromatic dianhydrides oranhydride acid chlorides.

The polymer described here was prepared by reaction of the diamine withthe dianhydride in N-methylpyrrolidone solution. The process involved atwo stage polymerization. During the first stage, a polyamic acid wasformed by reaction between the two starting materials. The second stagewas the chemical imidization of the amic acid groups using pyridine andacetic anhydride. The polymer inherent viscosities reported here weremeasured at 30° C. in NMP solution using aliquots of the reactionmixture diluted polymer concentration of 0.5 g/dL.

The starting materials, 4.11 g of 2,4-diamino-t-butylbenzene (0.0250mole) and 7.59 g 3,3',4,4'-tetracarboxybiphenyl dianhydride (0.0258mole), were weighed into a 200 mL reaction vessel. After purging thereaction vessel with nitrogen for 35 min, 100 mL of N-methylpyrrolidone,which had been cooled in an ethylene glycol/dry ice bath, was added tothe reaction vessel. The mixture was stirred and allowed to warm to roomtemperature. After 21.5 hrs, a 1.25 mL aliquot of the solution waswithdrawn, diluted to a total volume of 25 mL with NMP, and used todetermine the inherent viscosity of the polyamic acid (0.11 dL/g).Reaction was continued for 7.5 hrs, at which time the inherent viscositywas determined to be 0.20 dL/g. After an additional 17.2 hrs thepolyamic acid inherent viscosity measured 0.32 dL/g. The reactionmixture was then heated to 54° C. for 3 hrs after which the inherentviscosity of the polyamic acid was 0.17 dL/g. To the remainder of thereaction mixture, 5 mL of pyridine was added, and 30 min later 5 mL ofacetic anhydride was added. The stirring continued overnight. A 1.47 mLaliquot of the resulting polyimide solution was then diluted with enoughNMP to give a 25 mL total solution volume, and the inherent viscosity ofthe polyimide was determined to be 0.29 dL/g.

The fact that the product of the reaction was a homogeneous solutiondemonstrates that the polyimide made from 2,4-diamino-t-butylbenzene andbiphenyl dianhydride is soluble in NMP. The polyimide was precipitatedby pouring the reaction mixture into a solution of water and methanol inblender, separated from the liquid, refluxed in water/methanol for aboutthree hours, dried, and designated Example 14.

EXAMPLE 15

In this example a polyamide-imide polymer was made by reacting2,4-diamino-t-butylbenzene with trimellitic acid chloride inN,N'-dimethylacetamide.

The starting material, 8.22 g of 2,4-diamino-t-butylbenzene (0.05 mole)was weighed into a 100 mL reaction vessel and then dissolved in 56.23 gof N,N'-dimethyacetamide. During a 1.75 hr reaction period, smallincrements (1-2 g) of trimellitic acid chloride to total 10.53 g (0.05mole) were added to the solution which was maintained at a temperaturebelow 40° C. The reaction was continued for 6 hrs, at which time a solidwas precipitated from the reaction solution with water in a blender andrecovered by filtration. The inherent viscosity of this solid wasdetermined to be 0.08 dL/g.

A portion of the solid was placed in a 260° C. oven for 35 min, afterwhich the inherent viscosity of the polymer was 0.13 dL/g.

EXAMPLE 16

In a manner similar to Example 14 a polyimide polymer was made byreacting 1.514 g of 2,4-diamino-t-butylbenzene, with 4.096 g of2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane in 13.155 g ofN-methylpyrrolidone. The resulting polyamic acid had an inherentviscosity of 0.34 dL/g. A film cast from the polyamic acid and thermallyimidized had a glass transition temperature of 365° C.

Comparative Example A

A polyimide was prepared from oxybisaniline and3,3',4,4'-tetracarboxybenzophenone dianhydride in NMP by a methodsimilar to that described in the example, above. A 200 mL reactionvessel was used and the amounts of materials are listed below:

    ______________________________________                                        oxybisaniline       4.40 g (0.0220 mole)                                      benzophenone dianhydride                                                                          7.08 g (0.0220 mole)                                      NMP                 100 mL                                                    ______________________________________                                    

4.6 mL each of pyridine and acetic anhydride were used to chemicallyimidize the product. The inherent viscosity of the polyamic acid was1.27 dL/g. However, the inherent viscosity of the polyimide, which wasdesignated Example A, was not measured because this product gelled. Thebehavior of this polyimide demonstrates that one advantage polyimidescontaining 2,4-diamino-t-butylbenzene have over other polyimides isenhanced solubility in organic solvents.

EXAMPLE 17

Some physical properties of the polyamide, polyimide, andpolyamide-imide polymers of Examples 10-16 and A are given in Table IIbelow.

                  TABLE II                                                        ______________________________________                                        Polyamide, Polyimide, And Polyamide-imide                                     Polymers of 2,4-diamino-t-butylbenzene                                        Example                                                                              Acidic                T.sub.g                                                                            TGA (°C.)                            No.    Compound       IV     (°C.)                                                                       Nitrogen                                                                              Air                                 ______________________________________                                        10     terephthaloyl  0.41   331  373     352                                        chloride       0.86   334                                              11     isophthaloyl   0.24   283  383     346                                        chloride       0.51   292                                              12     5-t-butyl-     0.33   292  379     350                                        isophthaloyl   0.82   298                                                     chloride                                                               13     adipoyl        0.27   182  347     334                                        chloride       0.34   183                                              14     3,3',4,4'-tetra-                                                                             0.29   nd   477     428                                        carboxybiphenyl                                                               dianhydride                                                            15     trimellitic    0.13   nd   330     360                                        anhydride acid                                                                chloride                                                               16     6FDA           0.49   365  468     428                                 A      3,3',4,4'-tetra-                                                                             gel    275  544     516                                        carboxybenzo-                                                                 phenone dianhydride                                                    ______________________________________                                         IV = Inherent viscosities. The polyaramide inherent viscosities reported      here were measured at 30° C. in DMAC solution diluted to a polymer     concentration of 0.4 g/dL.                                                    TGA = Temperature at which 1% weight loss is found.                           nd = not detected                                                        

These results show the polyamide, polyimide, and polyamide-imidepolymers made from 2,4-diamino-t-butylbenzene can be used in film, fiberor coating application where the high temperature properties of thesetypes of polymers are needed. The solubility of these polymers willprovide improved processability. However, the effect of the t-butylmoiety is to raise the thermal properties of the polymer.

We claim:
 1. A resinous condensation polymer of a tricarboxylic acidcompound and a aromatic diprimary amine comprising adiamino-t-butylbenzene.
 2. The polymer of claim 1 wherein the diprimaryamine comprises at least one diamino-t-butylbenzene having amino groupsmeta or para to each other on the benzene ring.
 3. The polymer of claim2 comprising an at least partially soluble, film-forming polyamide-imideof at least one diamino-t-butylbenzene selected from the groupconsisting of 2,4-diamino-t-butylbenzene, 2,5-diamino-t-butylbenzene,2,6-diamino-t-butylbenzene, and 3,5-diamino-t-butylbenzene, and the acylchloride derivative of trimellitic acid anhydride.
 4. Thepolyamide-imide of claim 3 wherein the diamono-t-butylbenzene is2,4-diamino-t-butylbenzene.
 5. The polyamide-imide of claim 3 whereinthe diamino-t-butylbenzene is 3,5-diamino-t-butylbenzene.